Controlling bacteria with a fatty tetraamine

ABSTRACT

FATTY TETRAAMINES ARE USED ALONE OR IN ADMIXTURE WITH OTHER SPECIFIED COMPOUNDS AS BIOCIDES FOR VARIOUS PURPOSES.

United States Patent 015cc ABSTRACT OF THE DISCLOSURE Fatty tetraamines are used alone or in admixture with other specified compounds as biocides for various pur poses.

This invention relates to fatty tetraamines and their use as biocides. More particularly, this invention relates to the use of N"',N"-di-(3-aminopropyl) aminofattyamines as biocides.

Much effort has been expended to devise a biocide which is all-purpose. Usually, the biocide is useful against one or more aerobes or anaerobes, but never all of them.

With the recent advent of difunctional fatty compounds, particularly the dicarboxylic acids, chemists and bacteriologists have come closer to such a desire. Copending patent applications, Ser. No. 41,014 filed Nov. 9, 1964, now US. Pat. 3,448,374 issued Dec. 24, 1968, and Ser. No. 398,437 filed Sept. 22, 1964 now US. Pat. 3,354,213 issued Nov. 21, 1967, respectively, are typical examples of such recent work.

Accordingly, an object of this invention is to provide diamino fatty amines which are useful as biocides.

Another object is to provide bactericides which are useful against anaerobes.

Still another object is to provide bactericides which are useful for aerobes.

A further object is to provide novel sulfate reducer bactericides. 40

Other objects of the invention will in part be obvious and will in part appear hereinafter.

It has now been found that fatty tetraamines of the following formula may be used as biocides for anaerobes and aerobes:

FORMULA I where:

11:0 to 2 x+y=6 to 22 Among the fatty tetraamines which fall within the above formula are N",N"-di- 3-a'minopropyl) aminomethylcaprylylamine, N',N-di-( 3-aminopropyl) aminomethylcaprylamine, N"',N"-di- 3-aminopropyl aminomethyllaurylamine, N"',N-di- 3-aminopropyl aminomethylmyristylamine, N",N"-di- 3 -aminopropyl) aminomethylpalmitylamine, N",N"-di- 3-aminopropyl a'minomethylstearylamine, N"',N"-di- 3-aminopropyl) aminomethylarachidylamine, N"',N"-di- 3-aminopropyl) aminomethylbehenylamine, N,N"-di- 3-aminopropyl aminomethyllignocerylamine, N',N"-di- 3-aminopropyl) aminoethylcaprylylamine,

3,592,918 Patented July 13, 1971 N"',N"-di- 3-aminopropyl) aminoethylcaprylamine, N,N-di- 3-aminopropyl) aminoethyllaurylamine, N"',N"-di- 3-aminopropyl aminoethylmyristylamine, N",N"-di- 3-aminopropyl aminoethylpalmitylamine, N",N"-di- 3-aminopropyl aminoethylstearylamine, N"',N"-di- 3-aminopropyl) aminoethylarachidylamine, N",N-di-(3-aminopropyl) aminoethylbehenyl amine, N",N"-di- 3-aminopropyl aminoethyllignocerylamine,

or mixtures thereof such as derivable from natural fats and oils such as tallow, soybean oil and coconut oil.

The invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others, and the compound possessing the features, properties, and the relation of elements, which are exemplified in the following detailed disclosure, and the scope of the invention will be indicated in the claims.

Reference is now made to the following examples which illustrate the invention in detail:

EXAMPLE I A number of known biocides and the N"',N"-di-(3- aminopropyl)aminofattyamines are compared as to their algaecidal activity against chlamydomonas (C in Table 1 which follows( and scenedesmus (S). All results shown (expressed in ppm.) are of replicate testing with the highest dilution exhibiting growth and the lowest dilution inhibiting growth being reported as a range. All tests are run at room temperature, the chemical named being tested on an as is basis.

TABLE 1 Algae Chemical 0 S Zinc dimethyldithiocarbamate 5. 0-7. 5 5. 07. 'lributyltin oxide 10-15 10-1 'lributyltin chloride 5. 0-7. 5 5. 07. 5 N-alkyl(C1z, C14, C1a)dimethylbenzyl ammonium chloride 2. 5-5. 0 2. 5-5. 0 N -oleyltetrahydropyrimidone 2. 5 5. 040 N -dodecyl 3.3-imino-di-propionamide 2. 5-5. 0 10-20 N-[3octadecenylamine) propyl]xylylstearam e 1020 5-10 Copper sulfate 0. 11 0. 11 N,N-di-(3-aminopropyl)aminomethlystearylamine (DMSA) 0. 11 0. 11 Glutamate salt of DMSA" 0. 11 0. 46 Glutamate salt of N N-d aminoproply) aminococoamine 0. 15 0. 11

EXAMPLE II A common contaminant of oil injection systems is D- desulfricans, which is an anaerobic bacteria. In the Table 2 which follows, the named diamines and their salts (on an as-is basis) are compared to the named tetraamines and the results are expressed in a lower and upper effective range in a p.p.m. basis. The tests are run at 3132 C. for twenty-eight days in a 3.0% NaCl based media.

EXAMPLE III N",N"-di-(3 aminopropyl)aminomethylstearylamine (DMSA) exhibits synergistic bactericidal activity when employed in combination with a compound selected from 3 the group consisting of dimethylsulfoxide (DMSO) and the benzyl quaternary of dimethyl tertiary ,B-amine (BQDBA).

Following are the test data showing activity against both aerobic and anaerobic bacteria in water and in brine.

tion, are etficiently attained, and, since certain changes may be made in carrying out the above method and in the compounds set forth without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

TABLE 3 Minimum killing Compound Organism tested Diluent dose (p.p.m.)

liseulsiomonas aerugia msa 1U e10 actcr aerogems 10 DMSA (100%) Staphyloccoccus aurcus" 10 Bacillus cercus 5 D. desulfuricans (S-R Distilled l[; l0 Pseudomonas aeruginosa. 200 BQpgA n Aerobacter aerogenes. l0 Staphylococcus aureus 10 D. desu furicans (S-R 10 DMSO (100%) Distilled H2O... 100 DMSA (37.5%) Brine 100 DMSO (12.5%) Sulfate-reducers I1 0" 1 DMSA (37.5%) Brine H 20 BQDBA(12. H1O 1 D 13 (12.5 d0.'- Brine l0 DMSA (37. Aerobacler aeroyencsnfl 20 DMSO (12.5%) Pscudomonas aerugz'nosa Water (50%) DMSA (50%).. Aerobaclcr aerogevzesup B 80 Water (50%) 12.991331017101108 aeruginosa 80 MS 100 cro acler aerogenesnn 80 lfiseugomonas aeruginosa 88 era acler acrogcncs. s 8 BQDBA (100%) "{Pseudomonas aeruginosa 80 1 Exposure bottles containing sterile distilled water or sterile 3% synthetic brine are inoculated with the test organisms (aerobes)(slime formers) to make up a concentration of 200.000 organisms/ml. diluent (previously determined by plate counts). The chemical compounds are added to the exposure bottles at appropriate doses for 1 or 2 hours as indicated. After the exposure time, a 1 ml. sample from each bottle is transferred to Diicos sterile nutrient broth bottles and incubated at 37 C. for 78 days. Growth is determined by turbidity in the broth and cidal elfects are determined by subculturing in neutralizing broth and also by biochemical measurement of cell viability.

2 Inhibition of J). (lesulfuricans (sulfate-reducers) is determined by the procedure recommended by the American Petroleum Industry (1950). Exposure bottles containing either sterile distilled water or sterile 3% synthetic brine are inoculated with four day old cultures of D. desuljuricmzs in an anaerobic condition and exposed to the chemical compounds at appropriate doses for 1 or 2 hours as indicated. After the exposure time, a 1 ml. sample from each bottle is transferred to an anaerobic sulfate-reducing medium (API broth) and incubated at 37 C. for -20 days. Growth of sulfate-reducers in the bottles is indicated by blackening of the medium (red to black iron sulfide).

EXAMPLE IV N",N"-di-(3 aminopropylaminomethylstearylamine (DMSA) and homologs are very effective in controlling aerobic bacteria which are common contaminants in oil wells, cooling towers and swimming pools, as evidenced by the data of Table 4. All tests are run for 24 hours at 37 C.

It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention, which, as a matter of language, might be said to fall therebetween.

Now that the invention has been described:

What is claimed is:

1. A method of controlling bacteria comprising apply- TABLE 4 ing to said bacteria a bactericidal effective amount of a P 1 E 2 S 3 fatty tetraamine and derivatives falling within the followp.p.m. p.p.m. p.p.m. p.p. g formula: DMSA (1007 active) 5-10 5-10 5-10 2. 5-5. 0 N-cocotrimetllylene diamine e100 5045 50-75 25-50 CHKCHZ) CH (CH2) OH CHZCHZNHZ Alkyl dimethyl ethyl benzyl 5 CH ammonium chloride 100 100 100 100 2) Alkyl dimethylbenzyl am- Nil/II monium chloride I 1 P=Pseudomonas aerugi'nosa. (ing 2 E=E. coli. CH 3 S=Staphylococcus aureus. I 2 4 B=Bacillus cereu-Y v. mycoz'des. CH 5 Equal parts. I 2 The above data establishes that N, N-di-(3-amino- NH? propyl) aminomethylstearylamine is good as a microbiowhere logical control in industrial water systems and waterflood to 2 injection systems. It is also good as a microbioligical conx+y 6 to 22 trol 1n water-base mud systems as related to drilling and G5 The method of claim 1 wherein 01 to 500 ppm.

completion fluids where there is a high concentration of aerobic and anaerobic organisms. For disinfecting floors in hospitals, T.B. sanitariums, industries, gymnasiums, or home cellars where airborne micro-organisms may grow, AMSA is also effective. And, in dilute form, it would probably be good as an additive to some textiles or leather materials. It also functions as a paint preservative for water-base paints where there may be as incidence of protein-decomposing bacteria.

It will thus be seen that the objects set forth above, among those made apparent from the preceding descrip- 11/1967 Miller 260-5831 12/1968 Miller 260-583I JEROME D. GOLDBERG, Primary Examiner 

